JPH06263418A - Red diamond and pink diamond - Google Patents

Red diamond and pink diamond

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Publication number
JPH06263418A
JPH06263418A JP5053959A JP5395993A JPH06263418A JP H06263418 A JPH06263418 A JP H06263418A JP 5053959 A JP5053959 A JP 5053959A JP 5395993 A JP5395993 A JP 5395993A JP H06263418 A JPH06263418 A JP H06263418A
Authority
JP
Japan
Prior art keywords
diamond
center
red
pink
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP5053959A
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Japanese (ja)
Other versions
JP3314444B2 (en
Inventor
Shuichi Sato
周一 佐藤
Hitoshi Sumiya
均 角谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Electric Industries Ltd
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Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to JP05395993A priority Critical patent/JP3314444B2/en
Priority to EP94103535A priority patent/EP0615954A1/en
Priority to ZA941710A priority patent/ZA941710B/en
Publication of JPH06263418A publication Critical patent/JPH06263418A/en
Application granted granted Critical
Publication of JP3314444B2 publication Critical patent/JP3314444B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/20—Doping by irradiation with electromagnetic waves or by particle radiation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/26—Preparation
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

PURPOSE:To provide a red diamond and a pink diamond which have heretofore been not obtained in a conventional method. CONSTITUTION:The red diamond is >=0.1cm<-1> to <0.2cm<-1> in absorption coefficient in 500nm 1b type nitrogen, >=0.05cm<-1> to <1cm<-1> in absorption coefficient in 570nm absorption peak of N-V center and <=0.2cm<-1> in absorption coefficient in visible region of GRI center, H2 center, H3 center and H4 center. The pink diamond is <0.1cm<-1> in absorption coefficient in 500nm of 1b type nitrogen and >=0.005cm<-1> to <0.3cm<-1> in absorption coefficient in 570nm of N-V center.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】この発明は、たとえば装飾用途に
適した赤色ダイヤモンド、桃色ダイヤモンドおよびそれ
らの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to red diamonds, pink diamonds suitable for decorative purposes and a method for producing them.

【０００２】[0002]

【従来の技術】従来、着色ダイヤモンドを次のように得
ていた。すなわち、天然原石に電子線を照射し、その後
真空下でアニーリングを行なうことによって、天然原石
中に各種のカラーセンターを作製し、着色していた。カ
ラーセンターは、結晶中の窒素と、電子線照射で生じた
格子欠陥とがアニーリングによって結合して形成される
ものである。格子欠陥単独よりなるカラーセンターもあ
る。カラーセンターの種類は、窒素の凝集形態によって
決まる。各カラーセンターと色との関係を表１に示す。2. Description of the Related Art Conventionally, colored diamond has been obtained as follows. That is, by irradiating a natural rough stone with an electron beam and then annealing it in a vacuum, various color centers were produced in the natural rough stone and colored. The color center is formed by combining nitrogen in the crystal and lattice defects generated by electron beam irradiation by annealing. Some color centers consist of lattice defects alone. The type of color center is determined by the form of nitrogen aggregation. Table 1 shows the relationship between each color center and color.

【０００３】[0003]

【表１】 表１に示した各カラーセンターの作製方法およびそれら
の特性については、Reports on Progress Physics,John
Walker,第４２巻，１９７９年「ダイヤモンドの吸光と
発光」に記載されている。また、カラーセンター作製後
にダイヤモンドが実際に呈する色は、表１に示したカラ
ーセンターの色にダイヤモンド原石のオリジナルの色と
を重ね合せた色となる。[Table 1] For the manufacturing method of each color center and their characteristics shown in Table 1, see Reports on Progress Physics, John.
Walker, Vol. 42, 1979 "Diamond Absorption and Emission". Further, the color actually exhibited by the diamond after the color center is manufactured is a color obtained by superimposing the color of the color center shown in Table 1 on the original color of the rough diamond.

【０００４】天然ダイヤモンド原石のオリジナルの色
は、表２のように分類される。The original color of the natural diamond rough is classified as shown in Table 2.

【０００５】[0005]

【表２】 [Table 2]

【０００６】[0006]

【発明が解決しようとする課題】従来の方法では、天然
ダイヤモンドまたは合成ダイヤモンドにカラーセンター
を作製しても、赤色または桃色を呈するダイヤモンドを
得ることができなかった。天然に産出されるカラーダイ
ヤモンドの中には、ごく稀に桃色を呈するものがある
が、供給量、金額の点から事実上その入手が困難であっ
た。赤色ダイヤモンドに関しては、天然には全く産出さ
れず、存在していなかった。According to the conventional method, even if a color center is formed on a natural diamond or a synthetic diamond, a diamond showing red or pink cannot be obtained. Some of the naturally produced colored diamonds have a pink color, but it was difficult to obtain them due to the amount of supply and the amount of money. Red diamond was never produced in nature and did not exist.

【０００７】従来、合成ダイヤモンドまたは天然ダイヤ
モンドを赤色または桃色に着色できなかった理由を、以
下に記載する。The reason why synthetic diamond or natural diamond could not be colored red or pink in the past is described below.

【０００８】 どのような種類のカラーセンターを選
択し、またその濃度（吸収係数）をどの範囲に設定すべ
きかが不明だったこと。It was unclear what kind of color center should be selected and in what range its density (absorption coefficient) should be set.

【０００９】 ベースとなる原石の色を何色とすべき
かが不明だったこと。 どのような製造条件が必要かが不明だったこと。[0009] It was unclear what color should be the color of the base stone. It was unclear what manufacturing conditions were required.

【００１０】本発明の目的は、従来実質上存在していな
かった赤色ダイヤモンドまたは桃色ダイヤモンドを提供
することにある。It is an object of the present invention to provide red or pink diamonds that have not previously been substantially present.

【００１１】本発明の他の目的は、赤色ダイヤモンドま
たは桃色ダイヤモンドを製造するための方法を提供する
ことにある。Another object of the present invention is to provide a method for producing red or pink diamonds.

【００１２】[0012]

【課題を解決するための手段および作用効果】この発明
によって得られる赤色ダイヤモンドは、以下の特徴を備
える。The red diamond obtained by the present invention has the following features.

【００１３】 Ｉｂ型窒素の５００ｎｍにおける吸収
係数が０．１ｃｍ-1以上０．２ｃｍ -1未満である。Absorption of Ib-type nitrogen at 500 nm
Coefficient is 0.1 cm-10.2 cm or more -1Is less than.

【００１４】 Ｎ−Ｖセンターの吸収ピーク５７０ｎ
ｍにおける吸収係数が０．０５ｃｍ -1以上１ｃｍ-1未満
でである。Absorption peak 570n of NV center
Absorption coefficient at m is 0.05 cm -11 cm or more-1Less than
It is.

【００１５】 ＧＲ１センター、Ｈ２センター、Ｈ３
センターおよびＨ４センターの可視域における吸収係数
が０．２ｃｍ-1以下である。GR1 center, H2 center, H3
The absorption coefficient in the visible region of the center and the H4 center is 0.2 cm -1 or less.

【００１６】この発明によって得られる桃色ダイヤモン
ドは、以下の特徴を備える。 Ｉｂ型窒素の５００ｎｍにおける吸収係数が０．１
ｃｍ-1未満である。The pink diamond obtained by the present invention has the following features. The absorption coefficient of Ib-type nitrogen at 500 nm is 0.1.
It is less than cm -1 .

【００１７】 Ｎ−Ｖセンターの吸収ピーク５７０ｎ
ｍにおける吸収係数が０．００５ｃｍ-1以上０．３ｃｍ
-1未満である。570n absorption peak of NV center
Absorption coefficient at m is 0.005 cm -1 or more and 0.3 cm
It is less than -1 .

【００１８】本件発明者らは、赤色ダイヤモンドまたは
桃色ダイヤモンドを得るためには、カラーセンターとし
てＮ−Ｖセンターを用い、その濃度を極めて低くするこ
とが必要であることを見出した。The present inventors have found that in order to obtain a red diamond or a pink diamond, it is necessary to use an NV center as a color center and make its concentration extremely low.

【００１９】また、本件発明者らは、ベースとなる原石
の色は、桃色ダイヤモンドを得る場合には極力透明に近
い方がよく、赤色ダイヤモンドを得る場合には黄色味を
帯びている方がよいことを見出した。黄色味を帯びた原
石としては、カラーセンターとしてＮ−Ｖセンターのみ
を作製するＩｂ型窒素のみから形成される合成Ｉｂ型ダ
イヤモンドが最適である。Further, the present inventors prefer that the color of the rough stone as the base should be as transparent as possible when obtaining a pink diamond, and it should be yellowish when obtaining a red diamond. I found that. As a yellowish rough stone, a synthetic Ib-type diamond formed only from Ib-type nitrogen that produces only NV centers as a color center is optimal.

【００２０】最終的に得られるダイヤモンドの色と、Ｎ
−Ｖセンターの吸収ピーク５７０ｎｍにおける吸収係数
との関係を調査したところ、下記の結果が得られた。The color of the finally obtained diamond and N
When the relation with the absorption coefficient at −570 nm of the absorption peak of −V center was investigated, the following results were obtained.

【００２１】 桃色ダイヤモンドを得ようとする場
合、吸収係数が０．００５ｃｍ-1以上０．３ｃｍ-1未満
であれば桃色となった。吸収係数が０．００５ｃｍ-1未
満であればほとんど透明となり、０．３ｃｍ-1以上であ
れば紫色となった。When trying to obtain a pink diamond, if the absorption coefficient is 0.005 cm −1 or more and less than 0.3 cm −1 , it becomes pink. When the absorption coefficient was less than 0.005 cm -1 , it became almost transparent, and when it was 0.3 cm -1 or more, it became purple.

【００２２】 赤色ダイヤモンドを得ようとする場
合、吸収係数が０．０５ｃｍ-1以上１．０ｃｍ-1未満で
あれば赤色となった。吸収係数が０．０５ｃｍ-1未満で
あればベースとしての原石の色が目立つようになり赤色
を呈さなくなり、また１．０ｃｍ-1以上であれは紫色を
呈するようになった。[0022] In order to obtain a red diamond, the absorption coefficient became red if it is less than 0.05cm -1 more than 1.0cm -1. If the absorption coefficient is less than 0.05 cm -1 , the color of the rough stone as the base becomes noticeable and the red color does not appear, and if it is 1.0 cm -1 or more, the color becomes purple.

【００２３】Ｉｂ型窒素による吸収は、ベースとなる原
石を黄色に着色する作用がある。この作用は、桃色ダイ
ヤモンドを得る場合には不要であるので、Ｉｂ型窒素の
濃度は極力小さい方がよい。具体的には、桃色ダイヤモ
ンドを得る場合には、Ｉｂ型窒素の５００ｎｍにおける
吸収係数を０．１ｃｍ-1未満とする必要がある。この吸
収係数が０．１ｃｍ-1以上となれば、原石の色は黄色味
を帯びてくるか、または赤色を呈するようになった。The absorption by the type Ib nitrogen has the effect of coloring the base rough stone in yellow. Since this action is unnecessary when obtaining pink diamonds, it is preferable that the concentration of Ib-type nitrogen is as low as possible. Specifically, when obtaining pink diamond, the absorption coefficient of Ib-type nitrogen at 500 nm needs to be less than 0.1 cm −1 . When the absorption coefficient was 0.1 cm -1 or more, the color of the rough stone became yellowish or reddish.

【００２４】赤色ダイヤモンドを得る場合には、Ｎ−Ｖ
センターによって生じる色と、ベースとなる原石の黄色
とを重ね合せる必要がある。Ｉｂ型窒素の５００ｎｍに
おける吸収係数が０．１ｃｍ-1以上０．２ｃｍ-1未満で
あれば、最終的に得られるダイヤモンドの色は赤色を呈
するようになった。この吸収係数が０．１ｃｍ-1未満で
あれば紫色または桃色となり、０．２ｃｍ-1以上では黄
色味を帯びるようになった。To obtain a red diamond, NV
It is necessary to overlap the color generated by the center with the yellow color of the base gemstone. When the absorption coefficient of Ib-type nitrogen at 500 nm was 0.1 cm -1 or more and less than 0.2 cm -1 , the color of the finally obtained diamond became red. If this absorption coefficient is less than 0.1 cm -1 , it becomes purple or pink, and if it is 0.2 cm -1 or more, it becomes yellowish.

【００２５】赤色ダイヤモンドの場合、可視域で他の吸
収（ＧＲ１センター、Ｈ２センター、Ｈ３センター、Ｈ
４センターによる吸収）が入ると、赤色に濁りが生じて
鮮明感が減少する。鮮明感を維持するためには、この吸
収係数が０．２ｃｍ-1以下であることが重要である。In the case of red diamond, other absorption in the visible region (GR1 center, H2 center, H3 center, H
When absorbed by 4 centers), the red color becomes cloudy and the vividness decreases. In order to maintain a clear feeling, it is important that this absorption coefficient is 0.2 cm -1 or less.

【００２６】ベースとなる原石に硼素が含まれている
と、その原石に電子線または中性子線を照射した際、黒
色のセンターができ、全体が黒ずんでしまう。そのた
め、桃色ダイヤモンドを得る場合には、硼素含有量を５
×１０17原子／ｃｍ3 以下にするのが望ましく、赤色ダ
イヤモンドを得る場合には硼素含有量を１×１０18原子
／ｃｍ3 以下にするのが望ましい。When the raw ore as a base contains boron, a black center is formed when the raw ore is irradiated with an electron beam or a neutron beam, and the whole is darkened. Therefore, when obtaining a pink diamond, the boron content should be 5
It is desirable that the concentration is not more than × 10 17 atoms / cm 3 , and if a red diamond is to be obtained, the boron content is desirably not more than 1 × 10 18 atoms / cm 3 .

【００２７】上記赤色ダイヤモンドまたは桃色ダイヤモ
ンドをブリリアントカットすれば、装飾用として適した
ものとなる。Brilliant cutting of the red diamond or pink diamond makes it suitable for decoration.

【００２８】上述の赤色ダイヤモンドは、以下の工程を
経て製造される。 Ｉｂ型窒素の含有量が１×１０17以上４×１０18原
子／ｃｍ3 未満であり、硼素含有量が１×１０18原子／
ｃｍ3 以下である合成ダイヤモンド結晶を用意する工
程。The above red diamond is manufactured through the following steps. Ib type nitrogen content is 1 × 10 17 or more and less than 4 × 10 18 atoms / cm 3 , and boron content is 1 × 10 18 atoms / cm 3.
A step of preparing a synthetic diamond crystal having a size of cm 3 or less.

【００２９】 前記ダイヤモンド結晶に１〜１０Ｍｅ
Ｖのエネルギで２×１０15以上５×１０16電子／ｃｍ2
以下の密度の電子線を照射する工程。1-10 Me for the diamond crystal
2 × 10 15 or more at V energy 5 × 10 16 electrons / cm 2
A step of irradiating an electron beam having the following density.

【００３０】 電子線照射後に前記ダイヤモンド結晶
を１０-1Ｔｏｒｒ以下の真空雰囲気中または不活性ガス
雰囲気中において６００℃以上８００℃未満の温度で３
時間以上アニーリングする工程。After the electron beam irradiation, the diamond crystal is heated to a temperature of 600 ° C. or more and less than 800 ° C. in a vacuum atmosphere of 10 −1 Torr or less or an inert gas atmosphere,
The process of annealing for more than an hour.

【００３１】電子線を照射する代わりに、２×１０15〜
８×１０17個／ｃｍ2 の密度の範囲内で中性子線を照射
してもよい。Instead of irradiating with an electron beam, 2 × 10 15 to
You may irradiate with a neutron beam within the density range of 8 * 10 < 17 > piece / cm < 2 >.

【００３２】上述の桃色ダイヤモンドは、以下の工程を
経て製造される。 Ｉｂ型窒素の含有量が３×１０16原子／ｃｍ3 以上
８×１０17原子／ｃｍ 3 未満であり、硼素含有量が５×
１０17原子／ｃｍ3 以下である合成ダイヤモンド結晶を
用意する工程。The above-mentioned pink diamond has the following steps.
Manufactured. Ib type nitrogen content is 3 × 1016Atom / cm3that's all
8 x 1017Atom / cm 3And the boron content is 5 ×
1017Atom / cm3The synthetic diamond crystal that is
Step of preparing.

【００３３】 前記ダイヤモンド結晶に１〜１０Ｍｅ
Ｖのエネルギで、１×１０16〜１×１０18電子／ｃｍ2
の密度の電子線を照射する工程。1-10 Me for the diamond crystal
1 × 10 16 to 1 × 10 18 electrons / cm 2 with V energy
The step of irradiating the electron beam with the density of.

【００３４】 電子線照射後に前記ダイヤモンド結晶
を１０-1Ｔｏｒｒ以下の真空雰囲気中または不活性ガス
雰囲気中において８００〜１１００℃の温度で３時間以
上アニーリングする工程。After the electron beam irradiation, a step of annealing the diamond crystal in a vacuum atmosphere of 10 −1 Torr or less or in an inert gas atmosphere at a temperature of 800 to 1100 ° C. for 3 hours or more.

【００３５】上記工程のうち、電子線を照射する代わり
に、２×１０15〜８×１０17個／ｃｍ2 の密度の範囲内
で中性子線を照射してもよい。In the above steps, instead of irradiating with electron beam, neutron beam may be irradiated within a density range of 2 × 10 15 to 8 × 10 17 pieces / cm 2 .

【００３６】所定含有量のＩｂ型窒素と硼素とを含む合
成ダイヤモンド結晶に対して、電子線または中性子線を
照射することにより、結晶中に格子欠陥を作製する。そ
の後に所定の温度範囲でアニーリングすれば窒素原子と
格子欠陥とが結合しカラーセンターを作る。A synthetic diamond crystal containing a predetermined amount of Ib type nitrogen and boron is irradiated with an electron beam or a neutron beam to form a lattice defect in the crystal. Then, if annealing is performed within a predetermined temperature range, the nitrogen atom and the lattice defect are combined to form a color center.

【００３７】赤色ダイヤモンドを製造する場合に、電子
線照射密度を２×１０15以上５×１０16電子／ｃｍ2 以
下としたのは、この範囲内であれば電子線照射によって
格子欠陥を結晶全体にむらなく作れるからである。密度
が上記範囲よりも低い場合には、格子欠陥濃度が低くな
り所定濃度のカラーセンターを作ることができなくな
る。一方、密度が上記範囲よりも大きい場合には、最終
的に格子欠陥が残存し、灰色を呈するようになる。同様
な理由で、電子線の代わりに中性子線を照射する場合に
は、その密度は２×１０15〜８×１０17個／ｃｍ2 の範
囲とするのがよい。In the production of red diamond, the electron beam irradiation density is set to be not less than 2 × 10 15 and not more than 5 × 10 16 electrons / cm 2 within this range because lattice defects are caused by the electron beam irradiation in the entire crystal. This is because it can be made evenly. If the density is lower than the above range, the density of lattice defects becomes low and it becomes impossible to form a color center having a predetermined density. On the other hand, when the density is higher than the above range, the lattice defects finally remain and become gray. For the same reason, when the neutron beam is irradiated instead of the electron beam, the density is preferably in the range of 2 × 10 15 to 8 × 10 17 pieces / cm 2 .

【００３８】桃色ダイヤモンドを製造する場合には、最
適な電子線照射密度は１×１０16〜１×１０18電子／ｃ
ｍ2 の範囲である。電子線の代わりに中性子線を照射す
る場合には、その密度は２×１０15〜８×１０17個／ｃ
ｍ2 の範囲内である。When producing pink diamonds, the optimum electron beam irradiation density is 1 × 10 16 to 1 × 10 18 electrons / c.
It is in the range of m 2 . When neutron rays are irradiated instead of electron beams, the density is 2 × 10 15 to 8 × 10 17 pieces / c.
It is within the range of m 2 .

【００３９】赤色ダイヤモンドを製造する場合に、アニ
ーリングの条件を６００℃以上８００℃未満の温度で３
時間以上としたのは、この条件下であれば格子欠陥と窒
素原子とを効率的に結合させ得るからである。アニーリ
ングの温度が６００℃未満である場合、またはアニーリ
ングの時間が３時間未満である場合には、窒素原子と格
子欠陥との結合が弱くなり、目的の色を作ることができ
ない。一方、アニーリング温度が８００℃以上の場合に
は、一旦できたカラーセンターが消滅してしまい、ダイ
ヤモンドは紫色を呈するようになる。When manufacturing red diamond, the annealing condition is set to a temperature of 600 ° C. or more and less than 800 ° C.
The reason for setting the time longer than that is that the lattice defects and the nitrogen atoms can be efficiently bonded under this condition. When the annealing temperature is less than 600 ° C. or when the annealing time is less than 3 hours, the bond between the nitrogen atom and the lattice defect is weakened and the desired color cannot be produced. On the other hand, when the annealing temperature is 800 ° C. or higher, the color center once formed disappears and the diamond becomes purple.

【００４０】同様な理由で、桃色ダイヤモンドを製造す
る場合のアニーリングの最適条件は、８００〜１１００
℃の温度で３時間以上である。For the same reason, the optimum annealing condition for producing a pink diamond is 800 to 1100.
At a temperature of ℃ for 3 hours or more.

【００４１】１０-1Ｔｏｒｒ以下の真空雰囲気中または
不活性ガス雰囲気中でアニーリングするのは、高温下で
のダイヤモンドの酸化または黒鉛化を防止するためであ
る。Annealing in a vacuum atmosphere of 10 -1 Torr or less or in an inert gas atmosphere is for preventing oxidation or graphitization of diamond at a high temperature.

【００４２】こうして、この発明によれば、装飾用に適
した赤色ダイヤモンドまたは桃色ダイヤモンドを得るこ
とができる。Thus, according to the present invention, it is possible to obtain a red diamond or a pink diamond suitable for decoration.

【００４３】[0043]

【実施例】 実施例１ 超高圧装置を用いて、圧力５．５ＧＰａおよび温度１３
５０℃の条件下で温度差法により種結晶上に０．６〜
０．８カラットのダイヤモンドを合成した。この合成に
際し、溶媒としてＦｅ−Ｃｏ−Ａｌ系合金を用い、Ａｌ
の添加量を変化させることによって結晶中の窒素含有量
を変化させた。また、合金構成材料として純度の異なる
ものを種々に選択することによって結晶中の硼素含有量
を変化させた。Example 1 A pressure of 5.5 GPa and a temperature of 13 using an ultrahigh pressure apparatus.
0.6 ~ on the seed crystal by the temperature difference method under the condition of 50 ℃
A 0.8 carat diamond was synthesized. At the time of this synthesis, using a Fe-Co-Al-based alloy as a solvent,
The nitrogen content in the crystals was changed by changing the addition amount of. Further, the boron content in the crystal was changed by variously selecting alloy constituent materials having different purities.

【００４４】電子線照射に関しては、エネルギが１Ｍｅ
Ｖ、密度が１×１０18電子／ｃｍ2の条件で行なった。
アニーリングに関しては、Ａｒガス雰囲気中で温度が１
１００℃、時間が３時間の条件で行なった。Regarding the electron beam irradiation, the energy is 1 Me.
V, density was performed under the conditions of 1 × 10 18 electrons / cm 2.
Regarding annealing, the temperature is 1 in Ar gas atmosphere.
It was carried out under the conditions of 100 ° C. and time of 3 hours.

【００４５】合成した結晶を平板状に加工し、可視分光
光度計で５００ｎｍにおけるＩｂ型窒素の吸収係数およ
び５７０ｎｍにおけるＮ−Ｖセンターの吸収係数を測定
した。また、結晶中の窒素含有量をＥＳＲ装置で測定
し、硼素含有量をＳＩＭＳで測定した。その結果を、表
３に示す。The synthesized crystals were processed into a flat plate, and the absorption coefficient of Ib-type nitrogen at 500 nm and the absorption coefficient of NV center at 570 nm were measured with a visible spectrophotometer. Further, the nitrogen content in the crystal was measured by an ESR device, and the boron content was measured by SIMS. The results are shown in Table 3.

【００４６】[0046]

【表３】 [Table 3]

【００４７】実験Ｎｏ．２、３および４に該当するサン
プルをブリリアントカットしたところ、桃色を呈した美
しい装飾用ダイヤモンドになった。Experiment No. When the samples corresponding to Nos. 2, 3 and 4 were brilliant cut, they became beautiful ornamental diamonds of pink color.

【００４８】実験Ｎｏ．１〜４のサンプルについては、
Ｎ−Ｖセンターの存在のみが確認され、他のセンター
（Ｈ２センター、Ｈ３センターおよびＧＲ１センター）
の存在はなかった。Experiment No. For samples 1-4,
Only NV centers were confirmed, other centers (H2 center, H3 center and GR1 center)
There was no.

【００４９】電子線照射に代えて、２×１０15個／ｃｍ
2 の密度で中性子線の照射を行ない、同様の実験を行な
ったところ、同様の効果が得られた。2 × 10 15 pieces / cm instead of electron beam irradiation
When neutron irradiation was performed at a density of 2 and a similar experiment was performed, the same effect was obtained.

【００５０】実施例２ 超高圧装置を用いて圧力５．４ＧＰａ、温度１３８０℃
の条件下で種結晶上に０．７〜０８カラットのダイヤモ
ンドを合成した。溶媒としてＦｅ−Ｃｏ−Ａｌ系合金を
用い、Ａｌの添加量を変化させることによって結晶中の
窒素含有量を変化させた。Example 2 Using an ultrahigh pressure apparatus, pressure 5.4 GPa, temperature 1380 ° C.
A 0.7-08 carat diamond was synthesized on a seed crystal under the conditions of. The Fe-Co-Al-based alloy was used as the solvent, and the nitrogen content in the crystal was changed by changing the addition amount of Al.

【００５１】電子線の照射は、エネルギが１０ＭｅＶで
密度が１×１０16電子／ｃｍ2 の条件で行なった。アニ
ーリングは、１０-1Ｔｏｒｒの真空中で行なった。The electron beam irradiation was performed under the conditions of energy of 10 MeV and density of 1 × 10 16 electrons / cm 2 . Annealing was performed in a vacuum of 10 -1 Torr.

【００５２】窒素量および硼素量に関しては、実施例１
と同一の方法で測定した。測定結果を表４に示す。Regarding the amount of nitrogen and the amount of boron, Example 1 was used.
It was measured by the same method as. The measurement results are shown in Table 4.

【００５３】[0053]

【表４】 [Table 4]

【００５４】実験Ｎｏ．１２〜１４のサンプルをブリリ
アントカットしたところ、赤色を呈した美しい装飾ダイ
ヤモンドになった。Experiment No. When 12 to 14 samples were brilliant-cut, they became beautiful decorative diamonds of red color.

【００５５】電子線の照射に代えて、８×１０17個／ｃ
ｍ2 の密度で中性子線を照射し、上記と同様に実験を行
なったところ、同様の結果が得られた。8 × 10 17 pieces / c instead of electron beam irradiation
When a neutron beam was irradiated at a density of m 2 and an experiment was conducted in the same manner as above, the same result was obtained.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 Ｉｂ型窒素の５００ｎｍにおける吸収係
数が０．１ｃｍ-1以上０．２ｃｍ-1未満であり、 Ｎ−Ｖセンターの吸収ピーク５７０ｎｍにおける吸収係
数が０．０５ｃｍ-1以上１ｃｍ-1未満であり、 ＧＲ１センター、Ｈ２センター、Ｈ３センターおよびＨ
４センターの可視域における吸収係数が０．２ｃｍ-1以
下である、赤色ダイヤモンド。1. A type Ib absorption coefficient at 500nm of nitrogen is less than 0.1 cm -1 or more 0.2cm -1, N-V absorption coefficient at the absorption peak 570nm of center 0.05 cm -1 or more 1 cm -1 Less than, GR1 center, H2 center, H3 center and H
Red diamond having an absorption coefficient of 0.2 cm -1 or less in the visible region of 4 centers. 【請求項２】 硼素含有量が１×１０18原子／ｃｍ3 以
下である、請求項１に記載の赤色ダイヤモンド。2. The red diamond according to claim 1, having a boron content of 1 × 10 18 atoms / cm 3 or less. 【請求項３】 請求項１に記載の赤色ダイヤモンドをブ
リリアントカットした装飾用赤色ダイヤモンド。3. A decorative red diamond obtained by brilliant cutting the red diamond according to claim 1. 【請求項４】 Ｉｂ型窒素の５００ｎｍにおける吸収係
数が０．１ｃｍ-1未満であり、 Ｎ−Ｖセンターの吸収ピーク５７０ｎｍにおける吸収係
数が０．００５ｃｍ-1以上０．３ｃｍ-1未満である、桃
色ダイヤモンド。4. The absorption coefficient of Ib-type nitrogen at 500 nm is less than 0.1 cm −1 , and the absorption coefficient at an absorption peak of NV center at 570 nm is 0.005 cm −1 or more and less than 0.3 cm −1 . Pink diamond. 【請求項５】 硼素含有量が５×１０17原子／ｃｍ3 以
下である、請求項４に記載の桃色ダイヤモンド。5. The pink diamond according to claim 4, having a boron content of 5 × 10 17 atoms / cm 3 or less. 【請求項６】 請求項４に記載の桃色ダイヤモンドをブ
リリアントカットした装飾用桃色ダイヤモンド。6. An ornamental pink diamond obtained by brilliant cutting the pink diamond according to claim 4.
JP05395993A 1993-03-15 1993-03-15 Red and pink diamonds Expired - Lifetime JP3314444B2 (en)

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ZA941710A ZA941710B (en) 1993-03-15 1994-03-11 Red diamond pink diamond and method of producing the same

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